JP2008308552A - Adhesive composition and adhesive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition having excellent gap-filling properties, and providing a cured product having a low modulus and excellent adhesiveness, and to provide an adhesive film having an adhesive layer comprising the composition. <P>SOLUTION: The adhesive composition comprises (A) 100 pts.mass of a polyimide silicone resin obtained by reacting a diamine component with a carboxylic dianhydride component wherein the diamine component contains a diaminosiloxane, and the ratio of the total mol of the carboxylic dianhydride component to the total mol of the diamine component, or the ratio of the total mol of the diamine component to the total mol of the carboxylic dianhydride component in the reaction is 1.05 to 1.20, (B) 5-200 pts.mass of an epoxy resin and (C) a catalytic amount of an epoxy resin-curing catalyst. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an adhesive composition, and more particularly, to an adhesive composition and an adhesive film that include a polyimide silicone resin and an epoxy resin, and that can bond a semiconductor chip to a substrate without generating voids.

  In a semiconductor device, a large-diameter silicon wafer on which an IC circuit is formed is cut into semiconductor chips by a dicing process, and the chips are bonded by thermocompression bonding to a lead frame with a curable liquid adhesive (die bonding material) or the like. It is manufactured by curing (fixing) and fixing (mounting) the agent, and then wire-bonding between the electrodes and then sealing for handling and protection from the external environment. As this sealing form, a transfer molding method using a resin is most commonly used because it is excellent in mass productivity and inexpensive.

  In recent years, with higher functionality of semiconductor devices, the support base (base material) for mounting semiconductor chips is also required to have higher density and finer dimensions. If a liquid adhesive is used as the die bond material, the mounting of semiconductor chips Occasionally, the adhesive protrudes from the end of the chip to contaminate the electrode, or the chip is tilted due to the uneven thickness of the adhesive layer, resulting in a wire bond failure. Therefore, in order to improve these drawbacks, it has been desired to form an adhesive film.

  On the other hand, there are uneven portions due to circuit elements such as wiring on the substrate, and when a semiconductor chip is thermocompression bonded to such a substrate, an adhesive film (die bond film) as a die bond material may completely fill the recess. Otherwise, the unfilled portion remains as a void, which is heated in a reflow furnace and expands, and the adhesive layer may be destroyed to impair the reliability of the semiconductor device. In particular, in recent years, the temperature of reflow resistance corresponding to lead-free solder has also become high (265 ° C.), and the importance of preventing the formation of voids is increasing.

  In order to solve the above problem, it is conceivable that the semiconductor chip is thermocompression bonded with a die bond film having a low melt viscosity so as not to form voids as much as possible, but it is not perfect and requires a long time for thermocompression bonding. Or a high pressure is required. Furthermore, there is a problem that the die bond film protrudes greatly from the end of the chip and causes contamination of the electrodes. As another method, since molding with a sealing resin is performed at a high temperature and high pressure, there is a method of removing remaining voids in a resin sealing step. This method does not require a special process and is advantageous in terms of manufacturing. The present invention solves the problem of void formation by the latter method.

  Conventionally, a low elastic modulus material containing a resin having a siloxane structure introduced into polyimide or polyamideimide, which is a resin having excellent heat resistance, has been developed as the adhesive for die bonding. For example, siloxane-modified polyamideimide has been proposed. However, this does not have sufficient adhesion to the substrate.

  A composition in which a compound having two or more maleimide groups is blended with a siloxane-modified polyamideimide to improve high temperature characteristics has also been proposed (Patent Document 1). However, this composition is also inferior in adhesive strength.

In addition, it has been proposed to obtain an adhesive film having low elasticity and high adhesive force by using a polyimide resin having a phenolic hydroxyl group in the skeleton (for example, Patent Document 2). The adhesive film is obtained from a composition containing the polyimide resin and the epoxy resin, but the phenolic hydroxyl group is highly reactive with the epoxy group, and the polyimide resin is thermoplastic, so the obtained adhesive film is die-bonded. When used as a material, the melt viscosity of the adhesive film greatly increases due to the thermal history of the wire bonding step before the sealing step, making it difficult to remove voids in the resin sealing step.
Japanese Patent Laid-Open No. 10-60111 JP 2004-51794 A

  In the present invention, the increase in melt viscosity of the adhesive film due to the thermal history of the wire bonding process is suppressed, and voids can be removed in the resin sealing process, and hence the ability to fill the recesses on the substrate (hereinafter referred to as “gap fill performance”). It is an object of the present invention to provide an adhesive composition and an adhesive film that are excellent in adhesiveness.

  In an adhesive composition containing a polyimide silicone resin, the polyimide silicone resin has been conventionally obtained by reacting a diamine component and a carboxylic dianhydride component in an equimolar ratio. Have found that the above-mentioned object can be achieved by using a polyimide silicone resin produced by using either a diamine component or a carboxylic dianhydride component in excess of a specific amount.

That is, the present invention
(A) A polyimide silicone resin obtained by reacting a diamine component with a carboxylic acid dianhydride component, wherein the diamine component contains diaminopolysiloxane, and the carboxylic acid dianhydride component relative to the total molar amount of the diamine component in the reaction. 100 parts by mass of a polyimide silicone resin in which the ratio of the total molar amount of the diamine component or the ratio of the total molar amount of the diamine component to the total molar amount of the carboxylic dianhydride component is 1.05-1.20,
(B) Epoxy resin 5 to 200 parts by mass and (C) an adhesive composition containing a catalytic amount of an epoxy resin curing catalyst, and an adhesive film comprising an adhesive layer made of the adhesive composition.

  The adhesive film obtained by using the adhesive composition of the present invention has excellent gap fill performance, gives high adhesive strength to various substrates by heat curing, and has low elastic modulus and high heat resistance. It is useful for manufacturing a highly reliable semiconductor device.

  The adhesive composition of the present invention contains the above components (A) to (C), maintains its shape at room temperature, forms a film-like thin film, becomes plastic when heated, and is excellent by maintaining that state for a long time. The cured product has high adhesion and low elasticity to the substrate.

Each component will be described below.
The polyimide silicone resin as component (A) can contain a polyamic acid resin represented by the following general formula (3), which is a precursor thereof, but is water by imidization (dehydration ring closure) during heat curing in the die bonding step. As a by-product, peeling of the adhesive surface and the like may occur, a polyimide resin represented by the following general formula (4) that has been imidized (dehydrated and closed) in advance is preferable.

（式中、Ｘは芳香族環又は脂肪族環を含む四価の有機基であり、Ｙは二価の有機基であり、ｋは１〜３００の整数、好ましくは２〜３００の整数、特には５〜３００の整数であり、Ｙの少なくとも１はジオルガノポリシロキサン残基である。）

(Wherein X is a tetravalent organic group containing an aromatic ring or an aliphatic ring, Y is a divalent organic group, k is an integer from 1 to 300, preferably an integer from 2 to 300, especially Is an integer of 5 to 300, and at least one of Y is a diorganopolysiloxane residue.)

（式中、Ｘ、Ｙおよびｋは上記で定義した通りである。）

(Wherein X, Y and k are as defined above.)

  The polyamic acid resin represented by the general formula (3) is obtained by a reaction between a tetracarboxylic dianhydride component represented by the following structural formula (5) and a diamine component represented by the following structural formula (6). The polyimide resin represented by the general formula (4) can be obtained by dehydrating and ring-closing the polyamic acid resin obtained above by a conventional method.

（但し、Ｘは上記と同様の意味を示す。）

(However, X has the same meaning as described above.)

（但し、Ｙは上記と同様の意味を示す。）

(However, Y has the same meaning as described above.)

Conventionally, the reaction between the carboxylic acid dianhydride component and the diamine component is carried out by using an equimolar ratio (that is, a mole of 1.00 ± 0.01) in order to obtain a high molecular weight product from the viewpoint of the strength of the obtained resin. The component (A) in the present invention is obtained by using either one of a carboxylic dianhydride component and a diamine component in excess of a specific amount. It is obtained. That is, the component (A) is a ratio of the total molar amount of the carboxylic acid dianhydride component to the total molar amount of the diamine component or the total molar amount of the carboxylic acid dianhydride component. It is obtained by reacting in such an amount that the ratio of the total molar amount of the diamine component to the amount is 1.05-1.20, preferably 1.07-1.17, more preferably 1.07-1.15. Is. When the ratio exceeds the above upper limit, the strength of the cured product may decrease, it may be difficult to create a film from the composition, or it may be difficult to fill the void. If it is less than the lower limit (that is, the ratio is less than 1.0 to 1.05), the adhesive strength may be lowered.

  The tetracarboxylic dianhydride component represented by the above formula (5) includes, for example, the following, and these can be used alone or in combination of two or more.

  The diamine component represented by the above formula (6) can include various components, but in order to obtain the component (A) in the present invention, it is essential to include diaminopolysiloxane. The diaminopolysiloxane preferably has the following structural formula (1), and the amount thereof is the solubility of the resulting polyimide silicone resin in an organic solvent, the adhesion of the resulting composition to the substrate, and the low cured product. From the viewpoint of elastic modulus and flexibility, it is preferably 1 to 80 mol%, particularly 1 to 60 mol% of the total amount of the diamine component.

（式中、Ｒ³は炭素原子数３〜９の二価の有機基であり、Ｒ⁴は、互いに独立に、炭素原子数１〜８
の非置換又は置換の一価炭化水素基であり、ｊは１〜２００の整数である。）

(In the formula, R ³ is a divalent organic group having 3 to 9 carbon atoms, and R ⁴ is independently from 1 to 8 carbon atoms.
An unsubstituted or substituted monovalent hydrocarbon group, and j is an integer of 1 to 200. )

Examples of R ³ include — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —CH ₂ CH (CH ₃ ) —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₈ — and the like. Alkylene group, arylene group, for example

ベンジレン基等のアルキレン・アリーレン基、−（ＣＨ_２）_３−Ｏ−、−（ＣＨ_２）_４−Ｏ−等のオキシアルキレン基、オキシアリーレン基、例えば下記の基

Alkylene / arylene groups such as benzylene group, oxyalkylene groups such as — (CH ₂ ) ₃ —O—, — (CH ₂ ) ₄ —O—, oxyarylene groups, such as the following groups

及び、オキシアルキレン・アリーレン基、例えば下記の基

And oxyalkylene / arylene groups such as

などの二価炭化水素基が挙げられる。

And divalent hydrocarbon groups.

R ⁴ includes, for example, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, hexyl groups, cyclohexyl groups, 2-ethylhexyl groups, octyl groups and other alkyl groups, vinyl groups, etc. Allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, alkenyl group such as hexenyl group, aryl group such as phenyl group, tolyl group, xylyl group, aralkyl group such as benzyl group, phenylethyl group, etc. Groups in which some or all of the hydrogen atoms bonded to the carbon atoms of the group are substituted with halogen atoms such as fluorine, bromine, chlorine, etc., for example, chloromethyl group, bromoethyl group, 3,3,3-trifluoropropyl group And halogen-substituted alkyl groups such as methyl group and phenyl group are preferable. m is an integer of 1 to 200, preferably an integer of 1 to 100, more preferably an integer of 1 to 80.

Further, the diaminopolysiloxane preferably has the following structural formula (2) from the viewpoint of adhesiveness to the substrate.

（式中、Ｒ^３は上記で定義した通りであり、Ｒ^２はＲ^４と同じであるが、ただしビニル基およびフェニル基を除く。ｎは１以上の整数であり、ｍ、ｐおよびｑは０又は１以上の整数であり、ｎ＋ｍ＋ｐ＋ｑは１〜１００の整数である。）

(Wherein R ³ is as defined above and R ² is the same as R ⁴ except for a vinyl group and a phenyl group. N is an integer of 1 or more, and m, p and q are 0 or an integer of 1 or more, and n + m + p + q is an integer of 1 to 100.)

  The diaminopolysiloxane may be used alone or in combination of two or more as desired.

  Among the diamines represented by the above formula (6), examples of the diamine other than the diaminopolysiloxane include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenyl ether. 2,2′-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 1,4-bis (3-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 1,4-bis (p-aminophenylthioether) benzene 1,4-bis (m-aminophenylthioether) benzene, 2,2-bis 4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-amino) Phenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-aminophenoxy) phenyl] ethane, 1,1- Bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-amino Phenoxy) phenyl] methane, bis [3-methyl-4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [ , 5-Dimethyl-4- (4-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane Aromatic ring-containing diamines such as p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 1,4-bis (3-aminophenoxy) ) Benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-amino) Phenoxy) phenyl] propane and the like.

  The above diamines are not limited to these, and these diamines can be used alone or in combination of two or more as desired.

  The polyimide silicone resin can be produced according to a usual method. For example, a polyamic acid resin is synthesized by dissolving a tetracarboxylic dianhydride component and a diamine component having the above specific molar ratio in a solvent under an inert atmosphere, and reacting usually at 80 ° C. or less, preferably 0 to 40 ° C. Then, the polyamic acid resin obtained is heated to 100 to 200 ° C., preferably 150 to 200 ° C., to synthesize the desired polyimide silicone resin by dehydrating and ring-closing the acid amide portion of the polyamic acid resin. be able to.

  The organic solvent used for the reaction may not be one that can completely dissolve the starting material as long as it is inert to the resulting polyamic acid resin. Examples include tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and dimethyl sulfoxide, preferably aprotic Polar solvents, particularly preferably N-methylpyrrolidone, cyclohexanone and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

  In order to facilitate the dehydration ring closure, it is desirable to use an azeotropic dehydrating agent such as toluene or xylene. Further, dehydration ring closure can be performed at a low temperature using an acetic anhydride / pyridine mixed solution.

As the (B) epoxy resin used in the present invention, one having at least two epoxy groups in one molecule is preferable. Examples of such epoxy resins include, for example, bis (4-hydroxyphenyl) methane, 2,2′-bis (4-hydroxyphenyl) propane, or halides thereof, diglycidyl ethers and polycondensates thereof ( So-called bisphenol F type epoxy resin, bisphenol A type epoxy resin), butadiene diepoxide, vinylcyclohexene dioxide, diglycidyl ether of resorcin, 1,4-bis (2,3-epoxypropoxy) benzene, 4,4'-bis (2,3-epoxypropoxy) diphenyl ether, 1,4-bis (2,3-epoxypropoxy) cyclohexene, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 1,2-dioxybenzene or resorcinol , Polyphenol or poly Epoxy novolac obtained by condensing novolak type phenol resin (or halogenated novolak type phenol resin) such as epoxy glycidyl ether or polyglycidyl ester, phenol novolak, cresol novolak and the like obtained by condensing alcohol and epichlorohydrin and epichlorohydrin ( In other words, novolac type epoxy resin), epoxidized polyolefin epoxidized by peroxidation method, epoxidized polybutadiene, naphthalene ring-containing epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, cyclopentadiene type epoxy Resin etc. are mentioned.
Among these, an epoxy compound having an aromatic compound residue is preferable because it is easily compatible with the component (A).

  A monoepoxy compound may be appropriately used in combination, for example, styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide, dodecene oxide, etc. Can be mentioned. These epoxy resins may be used alone or in combination of two or more.

Furthermore, when the adhesive composition of the present invention is applied as an adhesive film and the silicon wafer to be attached is thin, the adhesive film can be pressed at a low temperature and low pressure to prevent the occurrence of cracks and warpage. B) The epoxy resin preferably has a liquid or softening temperature of 80 ° C or lower.

  (B) As for the compounding quantity of an epoxy resin, 5-200 mass parts is preferable with respect to 100 mass parts of (A) polyimide resin, and it is especially preferable that it is 10-100 mass parts. When the amount of the epoxy resin is less than the lower limit, the adhesive strength of the composition may be inferior. When the upper limit is exceeded, the elastic modulus of the adhesive layer may increase or the flexibility may be insufficient. .

  As the epoxy resin curing catalyst (C) used in the present invention, a known catalyst can be used, and examples thereof include a phosphorus catalyst and an amine catalyst.

（式中、Ｒ^８〜Ｒ^１５は水素原子又はフッ素、臭素、よう素などのハロゲン原子、あるいは炭素原子数１〜８のアルキル基、アルケニル基、アルキニル基、又は炭素原子数１〜８のアルコキシ基、トリフルオロメチル基、フェニル基などの非置換もしくは置換一価炭化水素基であり、総ての置換基が同一でも、おのおの異なっていても構わない。） Examples of the phosphorus catalyst include triphenylphosphine, triphenylphosphonium triphenylborate, tetraphenylphosphonium tetraphenylborate, and compounds as shown below.

(Wherein R ^{8 to} R ¹⁵ are a hydrogen atom, a halogen atom such as fluorine, bromine, iodine, or the like, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, an alkynyl group, or an alkoxy having 1 to 8 carbon atoms. A non-substituted or substituted monovalent hydrocarbon group such as a group, a trifluoromethyl group or a phenyl group, and all the substituents may be the same or different.)

Here, as the monovalent hydrocarbon group of R ^{8 to} R ¹⁵ , those similar to those exemplified for R ⁴ above, alkynyl groups such as ethynyl group, propynyl group, butynyl group, hexynyl group, and methoxy group, ethoxy group And alkoxy groups such as a group, propoxy group, isopropoxy group and butoxy group.

  Examples of the amine catalyst include imidazole derivatives such as dicyandiamide, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like. It is done.

Among these catalysts, particularly preferred catalysts are dicyandiamide and 2-phenyl-4,5-dihydroxymethylimidazole having a high melting point because of the storage stability of the adhesive composition of the present invention.

  These epoxy resin curing catalysts can be used alone or in combination of two or more. The compounding amount of the epoxy resin curing catalyst is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin. It is.

The composition of this invention may mix | blend the hardening | curing agent for epoxy resins. As the curing agent, various conventionally known ones can be used, such as diethylenetriamine, triethylenetetramine, diethylaminopropylamine, N-aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, Amine compounds such as metaxylylenediamine, menthanediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane; epoxy resin-diethylenetriamine adduct, amine -Modified aliphatic polyamines such as ethylene oxide adducts, cyanoethylated polyamines; bisphenol A, trimethylol allyloxyphenol, low polymerization degree phenol novolac resins, epoxidized or butylated phenol resins or Super Be ckcite 1001 (manufactured by Nippon Reichhold Chemical Co., Ltd.), Hitachi 4010 (manufactured by Hitachi, Ltd.), Scadoform L. A phenolic resin containing at least two phenolic hydroxyl groups in the molecule, such as a phenolic resin known under a trade name such as 9 (made by Scado Zwoll, the Netherlands) and Methylon 75108 (made by General Electric, USA); . 138 (manufactured by Nihon Reichhold Chemical Co., Ltd.), Melan (manufactured by Hitachi, Ltd.), U-Van 10R (manufactured by Toyo Kodan Kogyo Co., Ltd.), etc. , Amino resins such as aniline resins; 1 as shown by the formula HS (C ₂ H ₄ OCH ₂ OC ₂ H ₄ SS) _n C ₂ H ₄ OCH ₂ OC ₂ H ₄ SH (n = 1 to an integer of 1 to 10) Polysulfide resins having at least two mercapto groups in the molecule; organics such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, methyl nadic acid, dodecyl succinic anhydride, chlorendic anhydride An acid or an anhydride thereof (an acid anhydride) may be used. Among the curing agents described above, a phenolic resin (phenol novolac resin) is desirable because it provides good molding workability, provides excellent moisture resistance, is non-toxic and is relatively inexpensive. The above-mentioned curing agents are not necessarily limited to one type in use, and two or more types may be used in combination depending on the curing performance of the curing agents.

Although the usage-amount of this hardening | curing agent is suitably adjusted, generally it is 1-100 mass parts with respect to 100 mass parts of said epoxy resins, More typically, it is the range of 5-50 mass parts. If the amount of the curing agent used is less than 1 part by mass, it may be difficult to cure the composition of the present invention satisfactorily. May be diluted to require a long time for curing, and there may be a disadvantage that the physical properties of the cured product are lowered.

  Furthermore, in the composition of the present invention, silica or fine powder, alumina, titanium oxide, carbon black, conductive particles and other inorganic or organic fillers, pigments, dyes and other colorants, wetness to the extent that the properties are not impaired. Additives such as improvers, antioxidants, and heat stabilizers can be blended.

As the filler, silica particles and silicone fine particles having a particle diameter of 10 μm or less are preferable. The amount of the filler is 0 to 900 parts by mass, preferably 500 parts by mass or less, with respect to 100 parts by mass of the total amount of the components (A) to (C).

The silica particles moderately increase the melt viscosity of the adhesive layer, suppress the chip flow in the resin sealing step, and reduce the moisture absorption rate and the linear expansion coefficient of the cured product. The diameter is 10 μm, more preferably 5 μm or less, and the maximum particle diameter is 20 μm or less. If the average particle size exceeds this range, the smoothness of the surface of the adhesive film of the present invention may be impaired. The silica particles are preferably surface-treated with an organosilicon compound from the viewpoint of fluidity of the composition.

Silica particles include reinforcing properties such as fumed silica and precipitated silica, and crystalline silica such as silica quartz. Specifically, Aerosil R972, R974, R976, manufactured by Nippon Aerosil Co., Ltd., SE-2050, SC-2050, SC-2050, SE-1050, SO-E1, SO-C1, SO- from Admatechs Co., Ltd. Examples include E2, SO-C2, SO-E3, SO-C3, SO-E5, SO-C5, Musil 120A and Musil 130A manufactured by Shin-Etsu Chemical Co., Ltd., and a mixture thereof.

The blending amount of the silica particles is preferably 5 to 80% by mass, particularly 10 to 60% by mass, based on the total mass of the composition. If it is less than these ranges, the effect of lowering the moisture absorption rate and the linear expansion coefficient is lost, and if it exceeds, the elastic modulus may increase.

  As the silicone fine particles, composite silicone rubber fine particles are preferable. The composite silicone fine particles are particles in which microorganisms of a polyorganosilsesquioxane resin produced by polymerization on the surface are present on at least a part of the surface of the silicone rubber particles. By blending the composite silicone fine particles, it is possible to achieve a decrease in the elastic modulus and water absorption rate of the cured product in combination with the silica particles.

The composite silicone fine particles preferably have an average particle size of 0.1 to 10 μm, more preferably 0.5 to 5 μm. If the average particle size exceeds this range, the smoothness of the surface state of the adhesive film of the present invention may be impaired. Moreover, it is preferable that a maximum particle size is 20 micrometers or less, More preferably, it is 10 micrometers or less.

The compounding quantity of a composite silicone particle is 5-30 mass% of a composition total mass, Preferably it is 10-20 mass%. Outside these ranges, effects on the elastic modulus and water absorption of the cured product cannot be obtained, and the linear expansion coefficient of the cured product may increase and the strength may decrease.

The composite silicone fine particles can be prepared according to a method described in, for example, JP-A-7-196815. That is, an alkaline substance or an alkaline aqueous solution and an organotrialkoxysilane are added to an aqueous dispersion of spherical silicone rubber fine particles having an average particle size of 0.1 to 10 μm, and the organotrialkoxysilane is added on the surface of the spherical silicone rubber fine particles. Hydrolyze and polymerize, then dry it. The amount of the polyorganosilsesquioxane resin is preferably 1 to 500 parts by mass, more preferably 2 to 100 parts by mass with respect to 100 parts by mass of the silicone rubber spherical fine particles. If the amount is less than the lower limit, the dispersibility of the composite silicone fine particles in the adhesive composition may be deteriorated, and the film composition may be nonuniform. On the other hand, when it exceeds the said upper limit, there exists a tendency for the elasticity modulus of adhesive hardened | cured material to become high.

As the composite silicone fine particles, for example, KMP-600, KMP-605, X-52-7030 and the like manufactured by Shin-Etsu Chemical Co., Ltd. can be used. A mixture of two or more of these can also be used.

The adhesive composition of the present invention can be prepared by mixing the above components (A) to (C) and optionally other components at room temperature by conventional mixing means.

  The adhesive composition of the present invention can be used, for example, by dissolving the adhesive composition in an aprotic polar solvent such as toluene, cyclohexanone, or NMP at an appropriate concentration, coating the substrate, drying it, and applying the adhesive composition. Crimp the body and heat cure. In addition, an adhesive composition dissolved in an appropriate concentration in a solvent is applied onto a support substrate and dried to obtain a film in which an adhesive layer is formed (hereinafter referred to as an adhesive film), and this adhesive film is used as a substrate. It is also possible to bond by adhering to the adherend and heat curing. As the support substrate, polyethylene, polypropylene, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polytetrafluoroethylene, paper, metal foil or the like, or those obtained by releasing the surface can be used. .

  As drying conditions after apply | coating an adhesive composition, it is preferable to set it as normal temperature -200 degreeC, especially 80-150 degreeC for 1 minute-1 hour, especially 3-10 minutes. There is no restriction | limiting in particular in the film thickness of an adhesive bond layer, It can select according to the objective, Usually, it is 10-100 micrometers, Preferably it is 15-50 micrometers. Moreover, as the curing conditions for the adhesive layer, after pressure bonding at a pressure of 0.01 to 10 MPa, particularly 0.1 to 2 MPa, a temperature of 100 to 200 ° C., particularly 120 to 180 ° C., for 30 minutes to 5 hours, particularly 1 to It can be cured in 5 hours.

  The adhesive composition of the present invention can be used not only in the production of electronic parts such as semiconductor devices but also in various processes including an adhesion process, such as LED parts, sensors, and liquid crystal parts.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these Examples.

Synthesis of polyimide resin [Synthesis Example 1]
To a 1 L separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer, and a stirrer, 35.8 parts by mass of bis (3,4-dicarboxyphenyl) sulfone dianhydride and Then, 210 parts by mass of the solvent cyclohexanone was charged and stirred to disperse the acid anhydride.
In the dispersion, the following formula

で示されるジメチルジアミノポリシロキサン（以後、「ジアミノシロキサン−１」という。アミン当量が４８２である。）４４．９３質量部、をシクロヘキサノン５０質量部に分散させた溶液を滴下して、室温にて１時間撹拌反応させた後、更に２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン２１．７６質量部をシクロヘキサノン５０質量部に分散させた溶液を滴下して、室温にて１６時間撹拌反応させたることにより、アミック酸オリゴマーを合成した。該アミック酸オリゴマー溶液に、トルエン８０ｍｌを投入してから温度を上げ、約１７０℃で６時間還流させた。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認し、水分定量受器にたまっている流出液を除去しながら、１７０℃でトルエンを除去した。反応終了後、大過剰のメタノール中に得られた反応液を滴下してポリマーを析出させ、減圧乾燥してポリイミドシリコーン樹脂−１を得た。この合成では、カルボン酸二無水物成分の合計モル量に対するジアミン成分の合計モル量の比が１．０５であった。

A solution in which 44.93 parts by mass of dimethyldiaminopolysiloxane (hereinafter referred to as “diaminosiloxane-1”, amine equivalent is 482) dispersed in 50 parts by mass of cyclohexanone is added dropwise at room temperature. After agitation reaction for 1 hour, a solution in which 21.76 parts by mass of 2,2-bis (4- (4-aminophenoxy) phenyl) propane was dispersed in 50 parts by mass of cyclohexanone was added dropwise, and the mixture was stirred at room temperature for 16 hours. The amic acid oligomer was synthesized by stirring for a period of time. The amic acid oligomer solution was charged with 80 ml of toluene and then heated to reflux at about 170 ° C. for 6 hours. After confirming that a predetermined amount of water has accumulated in the moisture meter and that no water has flowed out, remove the effluent accumulated in the moisture meter and remove toluene at 170 ° C. did. After completion of the reaction, the reaction solution obtained in a large excess of methanol was added dropwise to precipitate a polymer and dried under reduced pressure to obtain polyimide silicone resin-1. In this synthesis, the ratio of the total molar amount of the diamine component to the total molar amount of the carboxylic dianhydride component was 1.05.

When the infrared absorption spectrum of the obtained resin was measured, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on an imide group was confirmed at 1780 cm ⁻¹ and 1720 cm ⁻¹ . It was 24,000 when the weight average molecular weight (polystyrene conversion) of this resin was measured by the gel permeation chromatography (GPC) which uses tetrahydrofuran as a solvent.

[Synthesis Example 2]
In Synthesis Example 1, except that 45.79 parts by mass of diaminosiloxane-1, 25.45 parts by mass of 2,2-bis (4- (4-aminophenoxy) phenyl) propane, and 320 parts by mass of cyclohexanone in total were used. Obtained polyimide silicone resin-2 according to Synthesis Example 1. The molecular weight was 15,000.
In this synthesis, the ratio of the total molar amount of the diamine component to the total molar amount of the carboxylic dianhydride component was 1.15.

[Synthesis Example 3]
In Synthesis Example 1, 37.59 parts by mass of bis (3,4-dicarboxyphenyl) sulfone dianhydride, 43.20 parts by mass of diaminosiloxane-1 and 2,2-bis (4- (4-aminophenoxy) Polyimide silicone resin-3 was obtained according to Synthesis Example 1 except that 20) 53 parts by mass of phenyl) propane and 310 parts by mass of cyclohexanone were used. The molecular weight was 22,000.
In this synthesis, the ratio of the total molar amount of the carboxylic dianhydride component to the total molar amount of the diamine component was 1.05.

[Synthesis Example 4]
In Synthesis Example 1, 41.17 parts by mass of bis (3,4-dicarboxyphenyl) sulfone dianhydride, 43.20 parts by mass of diaminosiloxane-1 and 2,2-bis (4- (4-aminophenoxy) Polyimide silicone resin-4 was obtained according to Synthesis Example 1 except that 20) 53 parts by mass of phenyl) propane and 320 parts by mass of cyclohexanone were used. The molecular weight was 22,000.
In this synthesis, the ratio of the total molar amount of the carboxylic dianhydride component to the total molar amount of the diamine component was 1.15.

[Synthesis Example 5]
In Synthesis Example 1, 39.38 parts by mass of bis (3,4-dicarboxyphenyl) sulfone dianhydride, 19.23 of all organic groups bonded to a silicon atom represented by the following formula instead of diaminosiloxane-1 64.60 parts by mass of 2,2-bis (4- (4-aminophenoxy) of phenylmethyldiaminopolysiloxane (hereinafter referred to as “diaminosiloxane-2”, amine equivalent of 1292) containing a mol% phenyl group A polyimide silicone resin-5 was obtained in the same manner as in Synthesis Example 1 except that 26.85 parts by mass of phenyl) propane and 390 parts by mass of cyclohexanone were used in total. The molecular weight was 19,000.
In this synthesis, the ratio of the total molar amount of the carboxylic dianhydride component to the total molar amount of the diamine component was 1.1.

[Comparative Synthesis Example 1]
In Synthesis Example 1, except that 43.20 parts by mass of diaminosiloxane-1, 20.53 parts by mass of 2,2-bis (4- (4-aminophenoxy) phenyl) propane, and 300 parts by mass of cyclohexanone in total were used. Obtained polyimide silicone resin-6 according to Synthesis Example 1. The molecular weight was 44,000.
In this synthesis, the ratio of the total molar amount of the diamine component to the total molar amount of the carboxylic dianhydride component was 1.0.

[Comparative Synthesis Example 2]
In Synthesis Example 1, 43.20 parts by mass of diaminosiloxane-1 and 43.20 parts by mass of 2,2-bis (4- (4-aminophenoxy) phenyl) propane as a diamine, a phenolic compound represented by the following formula A polyimide silicone resin-7 having a phenolic hydroxyl group in the molecular side chain was obtained according to Synthesis Example 1 except that 10.26 parts by mass of an aromatic diamine having a hydroxyl group and 290 parts by mass of cyclohexanone were used in total. . The molecular weight was 44,000.
In this synthesis, the ratio of the total molar amount of the diamine component to the total molar amount of the carboxylic dianhydride component was 1.0.

[Comparative Synthesis Example 3]
In Synthesis Example 1, except that 51.84 parts by mass of diaminosiloxane-1, 32.48 parts by mass of 2,2-bis (4- (4-aminophenoxy) phenyl) propane, and 360 parts by mass of cyclohexanone in total were used. Obtained polyimide silicone resin-8 according to Synthesis Example 1. The molecular weight was 4,800.
In this synthesis, the ratio of the total molar amount of the diamine component to the total molar amount of the carboxylic dianhydride component was 1.4.

Preparation of adhesive composition (Examples 1-6, Comparative Examples 1-3)
In each polyimide silicone resin solution, cyclohexanone such that the epoxy resin, catalyst, silica, and composite silicone rubber fine particles shown in Table 1 below are blended in amounts shown in the same table and the solid content concentration of the entire resin composition is 55 wt%. The mixture was mixed with a rotating / revolving mixer (manufactured by Shinky Co., Ltd.) to prepare an adhesive composition.

  Next, each composition that was allowed to stand for 24 hours was applied onto a PET film having a thickness of 50 μm coated with a fluorine-based silicone release agent, followed by heating and drying at 120 ° C. for 10 minutes to provide an adhesive layer having a thickness of about 25 μm. An adhesive film was prepared.

  Furthermore, the following test was done about each adhesive film. The results are shown in Table 1.

Young's modulus after curing The adhesive film obtained above was cured by heating at 175 ° C. for 2 hours. A 40 mm × 10 mm × 200 μm film was cut out to make a test piece, using a dynamic viscoelasticity measuring device, in a tensile mode, with a chuck distance of 10 mm, a measurement temperature of −80 ° C. to 300 ° C., and a measurement frequency of 1 Hz. It was measured.

Glass transition point and coefficient of linear expansion The adhesive film was heat treated at 175 ° C. for 2 hours, dried and cured. A 20 mm × 5 mm × 200 μm film was cut out to form a test piece, and the glass transition point and the linear expansion coefficient were measured. For the measurement, a thermomechanical measuring device, TMA-2000 (manufactured by ULVAC-RIKO) is used, and in the tension mode, the distance between chucks is 15 mm, the measurement temperature is −60 to 300 ° C., the temperature rising rate is 5 ° C./min, and the measurement load is 3 g. Measurements were made. In the linear expansion coefficient, α1 is a value in the temperature range below the glass transition point, and α2 is a value at a temperature above the glass transition point.

Adhesion test 450μm silicon wafer is diced into 2mm x 2mm chips, then the created adhesive film is thermocompression bonded to the backside of this silicon chip at 100 ° C, cut into chip shape, and silicon chip with adhesive film is attached Then, the chip was placed on a BT substrate and a silicon substrate on which a 10 mm × 10 mm resist AUS303 (manufactured by Unitechno Co., Ltd.) was applied and cured so that the surface to which the adhesive film was adhered was in contact with 170 ° C., 0 ° C. It was fixed by thermocompression bonding for 2 seconds under the condition of 1 MPa. The obtained test body was heated at 175 ° C. for 4 hours to cure the adhesive layer, thereby preparing a test piece. The shear adhesive strength at 260 ° C. was measured with a bond tester (manufactured by DAGE, 4000PXY).

A film (film thickness: 25 μm) of each resin composition was thermocompression-bonded at 70 ° C. on one surface of a transparent glass chip having a gap fill performance of 10 mm × 10 mm × 500 μm. The obtained transparent glass chip with an adhesive layer was die-bonded on a PCB having irregularities of 10 to 15 μm under the conditions of 130 ° C., 0.15 MPa, and 1 second so that the adhesive layer was in contact with the PCB. After die bonding, a heat history of 170 ° C. corresponding to the heat history of wire bond is added for 1 hour, and then pressed under the conditions of 175 ° C., 7 MPa, 90 seconds corresponding to EMC sealing. Observation was made to confirm whether voids of 10 to 15 μm were filled and voids were not formed. The case where no void was formed was marked with ◯, and the case where a void was formed was marked with x.

In Table 1 above, all blending amounts are solids. The materials used are as follows.
Materials Epoxy resin 1: RE-310S (manufactured by Nippon Kayaku Co., Ltd.), liquid epoxy resin epoxy resin 2: Epicoat 834 (manufactured by Japan Epoxy Resin Co., Ltd.), semi-solid, softening temperature 64 ° C.
Epoxy resin curing catalyst: Dicyandiamide (Japan Epoxy Resin)
Silica particles: SE-2050 (manufactured by Admatechs), spherical silica, average particle size 0.5 μm
Composite silicone rubber powder: X-52-7030 (manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.7 μm

  As shown in Table 1, the cured product of the adhesive film obtained from the composition of the present invention (Examples 1 to 6) has a higher adhesive force than the cured product of Comparative Example 1. In Comparative Example 2, as the component (A), a polyimide silicone resin having a molar ratio outside the scope of the present invention and having a phenolic hydroxyl group in the side chain is used. Since it has a phenolic hydroxyl group, the adhesiveness is good even if the molar ratio is outside the range of the present invention, but the gap fill performance is poor. When the composition of Comparative Example 3 was applied on a PET film to produce an adhesive film, repelling occurred and the adhesive film could not be produced. Therefore, an evaluation test could not be performed.

  The composition of the present invention provides a cured product having excellent gap fill properties, low elastic modulus and excellent adhesiveness, and is useful as an adhesive film in the production of highly reliable semiconductor devices.

Claims (7)

(A) A polyimide silicone resin obtained by reacting a diamine component with a carboxylic acid dianhydride component, wherein the diamine component contains diaminopolysiloxane, and the carboxylic acid dianhydride component relative to the total molar amount of the diamine component in the reaction. 100 parts by mass of a polyimide silicone resin in which the ratio of the total molar amount of the diamine component or the ratio of the total molar amount of the diamine component to the total molar amount of the carboxylic dianhydride component is 1.05-1.20,
(B) Epoxy resin An adhesive composition containing 5 to 200 parts by mass and (C) a catalytic amount of an epoxy resin curing catalyst. The adhesive composition according to claim 1, wherein the diaminopolysiloxane has a structure represented by the following formula (1).

(Wherein R ³ is a divalent organic group having 3 to 9 carbon atoms, R ⁴ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and j is It is an integer from 1 to 200.) The adhesive composition according to claim 1 or 2, wherein the component (B) has an aromatic compound residue. The adhesive composition of any one of Claims 1-3 which contains a filler in the quantity of 0-900 mass parts with respect to 100 mass parts of total amounts of (A)-(C) component. The adhesive composition according to claim 4, wherein the filler comprises silica particles and / or composite silicone rubber fine particles. (B) Adhesive composition of any one of Claims 1-5 in which the component contains the epoxy resin whose softening point measured by ring and ball method JIS-K7234 is 80 degrees C or less. The adhesive film provided with the contact bonding layer which consists of an adhesive composition of any one of Claims 1-6.